Process for the production of nonwoven fabrics containing binders

ABSTRACT

PRODUCTION OF NONWOVEN FABRICS BY APPLICATION ON A NONWOVEN OF AN AQUEOUS BINDER PREPARATION, WHICH CONTAINS AN EMULSIFIED BINDER AND A CATIONIC ADDITIVE (OBTAINED BY RETICULATION OF POLYAMINES OR POLYAMIDE-AMINES WITH BIFUNCTIONAL ALKYLATING OR ACYLATING AGENTS), AND CONDENSATION, THE SO PRODUCED NONWOVEN FABRICS BEING PARTICULARLY SUITABLE FOR BRIGHTENING DYEING AND PRINTING PROCESSES USING ANIONIC DYES AND ANIONIC FLUORESCENT BRIGHTENING AGENTS.

United States Patent C 3,767,395 PROCES FOR THE PRGDUCTIQN OF N ONWOVEN FABRICS (IONTAHNTNG BINDERS llanns Jenny, Aarau, and Georges Kieslinger, Basel, Switzerland, assignors to Sandoz Ltd. (also known as Sandoz AG), Basel, Switzerland No Drawing. Filed July 22, 1970, Ser. No. 57,314 Claims priority, application Switzerland, July 28, 1969, 11,457/69; Aug. 15, 1969, 12,412/69; Sept. 23, 1969, 14,315/69 Int. Cl. D06m 15/52, 15/60 US. Cl. 117-33.5 T 18 Claims ABSTRACT OF THE DISCLOSURE Production of nonwoven fabrics by application on a nonwoven of an aqueous binder preparation, which contains an emulsified binder and a cationic additive (obtained by reticulation of polyamines or polyamide-a'mines with bifunctional alkylating or acylating agents), and condensation, the so produced nonwoven fabrics being particularly suitable for brightening, dyeing and printing processes using anionic dyes and anionic fluorescent brightening agents.

The production of coloured nonwoven fabrics containing binders is known. Often, however, the manufacturer wishes to produce uncoloured bonded nonwovens which can be placed in store and dyed as and when required. With this in view the application of binder compositions containing agents which improve the dyeability of the binder has been recommended.

It has now been found that assistants especially suitable for this purpose are polyamines and polyamide-amines with recurrent cationic groupings, which are produced by crosslinking polyamines and/r polyamide-amines with bifunctional acylating or alkylating agents.

This invention is therefore directed to a process for the production of binder-containing nonwovens by impregnation and condensation, which is characterized in that the lap of fibrous material is impregnated with a liquor containing one or more of the aforesaid assistants in addition to the binder.

For this process it is preferable to use binders produced by emulsion polymerization, e.g. reaction in the presence of an emulsifier, unless the binders are self-emulsifying polymers. The choice of binder depends upon the properties which are desired of the final nonwoven, such as stiffness, suppleness, resilience, tensile strength and heat stability. Depending on the end-use of the nonwoven product, a wide variety of binders, some in the form of latices, can be used. They include e.g. polymers, copolymers and block polymers from acrylic acid or acrylic acid derivatives (e.g. acrylic acid ester and/or acrylonitrile), butadiene and styrene, e.g. from lower acrylic or methacrylic acid alkylesters, preferably those Whose alkyl radicals bear 1 to 4 carbon atoms and optionally acrylonitrile, or from mixtures of butadiene, styrene and acrylonitrile; from butadiene, acrylonitrile and methacrylic acid derivatives; from butadiene, styrene and optionally acrylonitrile or from lower acrylic acid alkylesters, styrene and acrylonitrile. Binders with a high content of acrylic acid derivatives are preferred.

The polyamines and polyamideamines containing recurrent cationic groupings are those synthesized by crosslinking of polyamines and/or polyamideamines with bivalent alkylating or acylating agents. These polymers are preferably so far crosslinked as to be at the limit of insolubility in water at room temperatures and they are best applied in the form of aqueous solutions.

3,707,395 Patented Dec. 26, 1972 'Polyarnines and polyamideamines which are particularly suitable are those which between the NH and/ or CO groups contain linear alkylene chains which have 2 to 8 carbon atoms and may bear lower alkyl radicals such as methyl, ethyl or benzene, e.g. phenyl, radicals. The alkylene chains are preferably unsubstituted and contain between the NH- groups preferably 2 to 4 carbon atoms and between the --CO groups preferably 4 to 8 carbon atoms.

The bivalent crosslinking alkylating and/or acylating agents are either symmetrical or asymmetrical, preferably linear monomeric or oligomeric compounds which may already bear cationic groups and/or may form quaternated groups by the alkylation. Alternatively the cationic groups may be present in the poly amideamine or polyamine.

Examples of suitable crosslinking polyamines are polyalkylene polyamines, for instance dipropylene triamine.

The following are suitable as crosslinking polyamide amines: the polymerization products of triethylene tetramine, tetraethylene pentamine, tri-(l,2-propylene)-tetramine, di-(1,3-propylene)-triamine and di-(l,4-butylene)- triamine with dicarboxylic acids of formula HOOC(CH COOH where m represents 4, 5, 6, 7 or 8, but preferably 4.

The suitable bifunctional crosslinking alkylating agents, which may bear cationic groups, are exemplified by epichlorohydrin and compounds of formula ZCH2N where 1: stands for a whole number from 0 to 7, Z for --CHCH2, -OH--CH2 or -CHCH2,

O H Cl H Br 0 Hz-Z R and R for lower alkyl or lower hydroxyalkyl, Y for an alkylene radical having 2 to 6 carbon atoms, a 2- hydroxy-l,3-propylene radical or one of the radicals CH -CH NHCONH-CH CH or As examples of suitable bifunctional acylating agents the chlorides of aliphatic dicarboxylic acids may be mentioned. It is of advantage to employ compounds of the type described in Belgian Patent 721,332, preferably cationic, water soluble polyamides which are formed by polyalkylation of polymers of formula with bifunctional alkylating agents of formula where A represents an anion, n 0 to 3 and Z one of the radicals -CHCH2 or -CHCH2 such as wool, hair and cellulose, synthetic fibres such as polyamides, polyesters and polyacrylonitrile, and regenerated fibres such as rayon, cellulose diacetate and cellulose triacetate, if desired with a proportion of an inorganic fibre such as glass fibre. After its formation the nonwoven is bonded by the application of a binder from an aqueous dispersion containing one of the aforcstated cationic additives and, if required, condensation and/or crosslinking assistants, optionally together with an acid or basic additive to stabilize the pH value.

The dispersions can be applied by any of the known methods e.g. by spraying, screen or foam impregnation techniques or by padding. In addition to the binder and if necessary an emulsifier, the dispersions contain an additive of cationic character as defined in the foregoing, which may be present in amounts of 0.09% to 7.5% or preferably 0.4% to 3% in relation to the solid content of the binder. (It is to be noted that the binder is employed preferably in the form of a preparation containing about 40-60% of the solid substance). Further, the dispersions may contain, as required, condensing agents and catalysts and an acid or basic additive such as an acid, a hydroxide or a buffering agent to maintain a constant pH value. The pH of the dispersion may be decidedly alkaline to decidedly acid, depending on its composition, although it is preferable to keep within the region of pH'7.5 to 10.5. In order to avoid precipitation the optimum pH must be determined with reference to the cationic additive and the binder present. If an acrylester based binder is used, the pH region of 7.5 to 10.5, preferably 8.6 to 9.6, is best for the additive described in Example 3.2 of Belgian Pat. 721,332.

The nonwovens are best impregnated at low to medium temperatures, e.g. at to 50 C. or more especially at 2530 C. The condensation is carried out with advantage at high temperatures, e.g. 100-180 C., the temperature being roughly in inverse relation to the time, which is about to 1 minute. The optimum condensation conditions are 2-3 minutes at 150 C.

Following application of the dispersion containing the binder and the cationic additive and condensation, the nonwoven can be coloured and/or optically brightened as desired. Nonwovens produced in accordance with the present process can be coloured and/or optically brightened by printing, exhaust dyeing or pad dyeing methods, i.e. the pad-steam, pad-roll, pad-batch and pad-jig processes. Dyes and optical brighteners of anionic character are used. Of the suitable optical brighteners may be mentioned those listed in the Colour Index, 1956, and Supplement 1963, in the section Fluorescent Brightening Agents and those described in Swiss Pat. 353,243. The suitable anionic dyes include those which form hetergpolar bonds with the cationic groupings of the additives used in this invention, e.g. dyes bearing sulphonic acid and/or carboxylic acid groups. They are found in the acid, direct, solubilized vat, reactive, premetallized and metallizable classes. Suitable dyes are described in the Colour Index, 1956, and Supplement 1963, in the sections Acid Dyes, Direct Dyes, Solubilized Vat Dyes, Reactive Dyes" and Mordant Dyes. Acid, direct and solubilized vat dyes are excellent for the present purpose.

The dyeings obtained on nonwovens produced in con formity with this invention are of considerably greater depth, and the optical brightening effects of greater intensity, than the dyeings and white effects obtained on material of the some composition but containing no additive of the disclosed type. The dyeings and effects are level and have good light, wet and rubbing fastness, the fastness to water and washing and the rubbing fastness being particularly good.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 A dispersion for pad application is prepared at pH 9.6

3O Thiourea 4 with 22.5 parts of water, 3 parts of a 30% aqueous solution of the compound described in Example 3.2 of Belgian Pat. 721,332, 05 part of ammonium nitrate, 0.28 part of 24% ammonia and 100 parts of a binder preparation produced by copolymerization of 36 parts of acrylic acid ethylester with 4 parts of acrylonitrile in the presence of 3 parts of the reaction product of 1 mole of nonylphenol with 12 moles of ethylene oxide, 0.5 part of potassium persulphate and 0.2 part of sodium bisulphite in 56.3 parts of water.

The dispersion is padded on a nonwoven of rayon staple and polyester fibre at 30 with an expression giving an increase of 65% over the dry weight. It is dried at 110, condensed for 2 minutes 30 seconds at 150, rinsed with cold water and then with water at 60, and dried.

On a roller printing machine the nonwoven fabric is printed from rollers engraved to 280 microns depth with a paste of the following composition:

Parts Sodium 1 (2'-chlorophenyl)-3-methyl-4-[3-(4"'- chloro 6" phenylamino 1",3 triazinyl- 2"'-amino)-phenylazo] 5 pyrazolone-5',6"-disulphonate Urea n-Butyl-diethyleneglycolether Hot water An 11% locust bean thickening solution Ammonium sulphate (33% solution) Nonylphenyl pentaglycolether The printed nonwoven fabric is dried at 110 and steamed for 30 minutes at 102-103". It is then washed off for 5 minutes at room temperature, for 5 minutes at 40 and for 5 minutes at each time with a 0.025% aqueous solution of the product of the addition reaction of 8 moles of ethylene oxide on 1 mole of oleyldiethylene triamine, partially quaternated with 1 mole of dimethyl sulphate.

The resulting yellow print is of one and half times greater depth than a comparative print on a nonwoven of the same composition produced without the additive conforming to this invention, and is faster to Wet treatments, such as the severe water fastness test and the wash fastness test at 40.

EXAMPLE 2 A dispersion is prepared at pH 9.8 with 100 parts of the binder preparations specified in Example 1, 3 parts of a 30% aqueous solution of the compound described in Example 3.2 of Belgian Pat. 721,332, 0.28 part of 24% ammonia and 19.1 parts of water. A nonwoven of rayon staple and polyester fibre is padded with the dispersion at 30 and an expression giving an increase of over the dry weight. It is dried at 110, cured, i.e. condensed, for 2 minutes 30 seconds at 150 and rinsed consecutively with cold and warm (60) water.

The nonwoven fabric is next padded at 30 and a pickup of 50% with a liquor containing 20 parts of the sodium salt of l(2',5'-dichlorophenyl)-3-methyl-4-(3"-trichloropyrimidylaminophenylazo) 5 pyrazolone-4,6"- disulphonic acid, parts of urea, 2 parts of sodium alginate, 20 parts of ammonium sulphate and 858 parts of water, totalling 1000 parts. It is then steamed for 15 minutes at rinsed first with cold water, then with water at 60, and washed otf at 60 with a 0.1% aqueous solution of a partially carboxymethylated alkylpolyglycolether.

A yellow dyeing is obtained on the nonwoven fabric which is of about 50% greater depth than a comparable dyeing produced by the same method on an identical nonwoven not containing the additive according to this invention. It has better fastness to wet treatments (the severe water fastness test and the wash test at 40).

EXAMPLE 3 A nonwoven fabric produced in accordance with Example 2 is printed with a paste of the following composition:

The print is aftertreated as described in Example 1. In comparison with a nonwoven fabric printed by the same method but produced without the additive of this invention, the yellow print is about five times greater in depth and has better fastness to wet treatments (the severe water fastness test and Washing at 40 EXAMPLE 4 The procedure of Example 3 is followed, except that the dye used is 24 parts of the sodium salt of 1-[4'-(5"- ohloro 2", "-difiuoropyrimidyl-4"amino) phenylazo1- 2-amino 8 hydroxy-naphthalene-6,2'-disulphonic acid. A red print is obtained which is of four times greater depth than a comparative print on the same nonwoven fabric produced without the additive of this invention. It is also faster to wet treatments such as water (the severe fastness test) and washing at 40.

EXAMPLE 5 The procedure is again as in Example 3, with the dye changed to 24 parts of the sodium salt of 1-amino-4-[3'- (5" chloro-2",6"-difluoropyrimidyl-4"-amino)-4'-methylphenylamino] anthraquinone-2,6-disu1phonic acid. A print of full blue shade is obtained which is two and a half times deeper than a comparative print produced by the same method on the nonwoven without the additive conforming to this invention. It has superior wet fastness properties.

EXAMPLE 6 A nonwoven fabric produced as described in Example 2 is padded with a solution of 6.5 g./l. sodium 4,4'-bis- (6" phenylamino-4"-B-amino carbonylethylamino-l", 3",5" triazinyl-2"-am1ino)-1,1'-sti1bene-2,2-disulphonate at 30 and an expression giving a 65% increase over the dry weight. The nonwoven is steamed for 15 minutes at 105, rinsed with cold water and then with water at 60 and dried.

The nonwoven, optically brightened by this pad-steam method, shows a significantly higher degree of whiteness both in daylight and ultraviolet light than a nonwoven optically brightened in the same way but prepared without the additive of this invention.

EXAMPLE 7 A padding liquor is prepared at pH 8.6 with 3 parts of a 30% aqueous solution of the compound described in Example 3.2. of Belgian Pat. 721,332., 0.5 part of ammonium nitrate, 0.28 part of 24% ammonia, 23.2 parts of water and, 100 parts of a binder preparation produced by copolymerization of 36 parts of acrylic acid ethylester with 4 parts of acrylonitrile in the presence of 3 parts of the reaction product of 1 mole of nonylphenol with 12 moles of ethylene oxide, 0.5 part of potassium persulphate and 0.2 part of sodium bisulphite in 56.3 parts of water.

A nonwoven of rayon staple and polyester fibre is padded with this liquor at 30 and an expression giving a 65% increase over the dry weight, dried at 110 and cured for 2 minutes 30 seconds at 150. Rinsing with cold and warm (60) water and drying complete this stage of the process.

The nonwoven fabric is padded at 30 and a pick-up of 50% with a liquor consisting of:

Parts Sodium salt of symmetrical bis-[2-methoxy-4-(3- sulphophenylazo)-phenyl]-urea 15 Urea Sodium alginate 2 Water 883 It is steamed for 15 minutes at rinsed with cold water and then with water at 60 and washed off with a 0.1% aqueous solution of a partially carboxymethylated alkylpolyglycolether.

A yellow dyeing is obtained which is twice as deep as a comparative dyeing on a nonwoven not containing the disclosed additive, and it is faster to wet treatments.

EXAMPLE 8 A nonwoven fabric produced as detailed in Example 7 is padded with a liquor consisting of:

Parts Sodium salt of 4-(2"-amino-8-hydroxynaphthyl- 1"-azo)-2,2'-dimethyl 4' dodecyloxycarboxylamino-1,1-diphenyl-5,6"-disulphonic acid 24 Urea 100 Sodium alginate 2 Water 874 and aftertreated as given in Example 7.

A red dyeing with good fastness properties is obtained which is of three times greater depth than the dyeing on a comparable nonwoven fabric produced without the additive of this invention.

EXAMPLE 9 A nonwoven produced as given in Example 7 is padded by the method of that example with a liquor consisting of:

The resulting blue dyeing is three times deeper than a comparative dyeing on a nonwoven fabric produced without the additive of this invention.

EXAMPLE 10 A polyester nonwoven is treated and dyed as described in Example 8. A red dyeing with good fastness properties is obtained which is twice as deep as a comparative dyeing on the nonwoven produced without the disclosed additive.

EXAMPLE 11 A padding liquor is prepared at pH 8.6 with 23.2 parts of water, 0.28 part of 24% ammonia, 0.5 part of ammonium nitrate, 3 parts of a 30% aqueous solution of the compound described in Example 3.2 of Belgian Pat. 721,332 and 100 parts of a binder preparation produced by copolymerization of 30 parts of acrylic acid butylester with 8 parts of acrylic acid ethylester and 2 parts of acrylonitrile in the presence of 4 parts of the reaction product of 1 mole of octylphenol with 15 moles of ethylene oxide, 0.3 part of potassium persulphate and 0.12 part of sodium bisulphite in 55.58 parts of water.

A nonwoven of rayon staple and polyester fibre is padded with this liquor as given in Example 7. The nonwoven fabric is than padded at 30 and a pick-up of 50% with a liquor consisting of and the dyeing fixed by dry heat treatment for minutes at 150. The red dyeing obtained has excellent wet fastness properties and is of six times greater depth than a comparative dyeing on a nonwoven fabric which does not contain the additive of this invention.

EXAMPLE 12 The nonwoven fabric is steamed for 5 minutes at 105 for fixation of the dyeing. This is of navy shade, has good fastness properties and is twice as deep as the comparative dyeing on a nonwoven fabric containing no additive of the disclosed type.

EXAMPLE 13 A nonwoven fabric of polyamide fibre, produced as in Example 7, is padded at 30 and an expression giving a 75% increase on the dry weight with a liquor of the following composition:

Parts Dye CI. 59826 (Solubilized Vat Green 1) Sodium nitrite 6 50% aqueous solution of a mixture of 25 parts of octylphenoldecaglycolether and 5 parts of oleylpolypeptide 2 Water 982 The dyeing is developed by treatment for seconds at 70 in a bath of 980 parts of water, 36 parts of 98% sulphuric acid and 1 part of a mixture of 80 parts of sodium ligninsulphonate, 10 parts of hydroquinone and 10 parts of tridecylbenzimidazole sulphonate. The nonwoven is then rinsed and washed off for 5 minutes at 80 in an aqueous solution of 0.1% of a partially carboxymethylated alkylpolyglycolether and 0.25% sodium tripolyphosphate.

The procedure results in a green dyeing which is of four times greater depth than a comparative dyeing on the nonwoven fabric made without the disclosed additive. The light fastness of the former dyeing is 6-7 (assessed on the blue scale), the water fastness 5 (severe test), the wash fastness at 60 4-5 and the rubbing fastness 4.

EXAMPLE 14 A polyester nonwoven is padded at 30 and a pick up of 180% with a liquor consisting of 39 parts of water,

0.9 part of 24% ammonia, 0.5 part of ammonium nitrate, 3 parts of a 30% aqueous solution of the reaction product of dipropylene triamine and epichlorohydrin as disclosed in German published patent application 1,213,226 and parts of the binder preparation as used in Example 1. It is dried at condensed for 5 minutes at rinsed with cold and warm water and dried.

The nonwoven fabric is next padded at 30 and an expression giving a 75 increase on the dry weight with a liquor of the following composition:

Parts Sodium salt of 1,4-bis-(2',4',6'-trimethyl-3'-bromo- 5-sulphophenylamino)-anthraquinone 15 Urea 100 Ammonium sulphate 20 Sodium alginate 2 Water 863 This is followed by steam fixation for 15 minutes at 105, cold and warm rinsing, washing off for 5 minutes at 60 with a 0.1% aqueous solution of a partially carboxymethylated alkylpolyglycolether, a final cold and warm rinse and drying. The resulting blue dyeing on the nonwoven fabric containing the additive is of intense depth, whereas the same substrate produced without the disclosed additive is no more than lightly dyed or tinted. The former dyeing has very good fastness to water and washing at 60.

Having thus disclosed the invention what we claim is:

1. A process for the production of brightened nonwoven fabrics containing resinous binders which comprises, in the following order, the steps of (1) impregnating a nonwoven fabric with a liquor containing a resinous binder and a water soluble polyamine or polyamide amine bearing recurring cationic groupings and produced by the crosslinking of polyamines or polyamide amines with bifunctional acylating or al-kylating agents, (2) effecting condensation and (3) subsequently optically brightening with an anionic fluorescent brightening agent the thustreated nonwoven fabric.

2. A process for the production of colored or brightened nonwoven fabrics containing resinous binders which comprises, in the following order, the steps of (1) impregnating a nonwoven fabric with a liquor containing a resinous binder and 0.09% to 7.5% in relation to the dry weight of the binder, of a water soluble polyamine or polyamide amine bearing recurring cationic groupings and produced by the cross-linking of polyamines or polyamide amines with bifunctional acylating or alkylating agents, (2) effecting condensation and (3) subsequently subjecting the thus-treated fabric to exhaust or pad dyeing with an anionic dye or to optical brightening with an anionic optical brightener or to both dyeing with an anionic dye and optical brightening with an anionic optical brightener.

3. The process of claim 2 wherein the anionic dyes and anionic optical brighteners contain carboxylic acid or sulphonic acid groups.

4. A process for the production of colored or brightened nonwoven fabrics containing resinous binders which comprises, in the following order, the steps of (1) impregnating a nonwoven fabric with a liquor containing a resinous binder and a water soluble polyamideamine bearing recurring cationic groupings and produced by the crosslinking polyamide amines having alkylene chains of 2 to 4 carbon atoms between the -NH- groups and alkylene chains of 4 to 8 carbon atoms between the -CO- groups with bifunctional acylating or alkylating agents, (2) effecting condensation and (3) subsequently subjecting the thus-treated fabric to printing or dyeing with an anionic dye or to optical brightem ing with an anionic optical brightener or to both printing or dyeing with an anionic dye and optical brightening with an anionic optical brightener.

The process of claim 4 wherein the nonwoven fabric with bifunctional alkylating agents of formula is impregnated with a liquor containing a polyamide- CH8 OH: I- HO CH8 ahulrrizcgpiclilrcelrlifiby polyalkylatlon of polymer contamrng CHPZ HN-CH CH NH-CH CH NHCO(CH CO 5 fi J with epichlorohydrin or a compound of the formula where A stands for an anion, n for 0 to 3 and Z for R1 R2 R1 Ila l one of the radicals -g R -g; CHZ-Z 10 -CH;CH1 or CHCH: where x stands for a whole number from 0 to 7, Z for O 0H 01 -CHCH, CHCH or OHCH are employed 2 z 7 15. A process as 1n claim 5, m which the binder prep- 0 0H 01 H Br arations are used in the form of emulsions. R and R for lower alkyl or lower hydroxyalkyl, Y for 16. A process according to claim 5, in which a nonan alkylene radical havi g 2 t0 6 c fi atoms, f woven fabric is impregnated with an aqueous emulsion hydroxy-1,3-propylene radical or one of the radicals containing in addition to an ethylacrylate/acrylonitrile CH CH -NH--CONHCH -CH or copolymer binder a cationic water soluble polyamide produced by the polyalkylation of a polymer of formula NHCH --CH CH- HNCH CH -NHC-H 6. The process of claim 5 wherein the condensation is CH2 NH CO (CHZ)4 COMN effected at elevated temperatures. with an alkylating agent of formula CH3 CH: CH: CH;

Cl-CHa-CHOHCH2N-CHzCHOHCH2NCHz-CHOHOHz-Cl 7. The process of claim 6 wherein the condensation 17. A process according to claim 5, in which a nonis carried out at a temperature of 100 to 180 C. woven fabric is impregnated with an aqueous emulsion 8. The process of claim 7 wherein the condensation containing in addition to an ethyl acrylate/butyl acrylate/ is carried out for a period ranging from about 15 mlnutes acrylonitrile copolymer binder a cationic water soluble to about 1 minute. polyamide produced by the polyalkylation of a polymer 9. A process as in claim 5, in which acrylate derivatives of formula are used as binders.

10. The process of claim 9 in which the liquor contains NWHN CH2 CHFNH CH2 CH2 0.09% to 7.5%, in relation to the dry weight of the QQ( 2)4 binder, of the polyamide amine and has a pH in the 40 with an alkylating agent of formula CH; CH; CH: CH;

C1-CHr-CHOHCHzN-CHa-GHOH-CHz-N-CHg-GHOH-CHr-Cl 69 e e 9 c1 01 range of 7.5 to 10.5 and the impregnated fabric is heated 18. The process of claim 4 wherein the nonwoven to a temperature in the range 100' to 180 C. for a period fabric is dyed with a direct dye or an acid dye. of 15 minutes to 1 minute.

11. The nonwoven fabric produced by the process of References Cited 1"; l 5 hi h b d UNITED STATES PATENTS process as in 0 arm in w c m er preparations which contain 0.09% to 7.5%, in relation to the fi giif f i 'g g2 dry weight of the binder, of the polyamide amine con- 3,278,560 10/1966 Gaermer 26 MN taining recurring cationic groupings are employed.

13. A process as in claim 5, in which binder preparations which contain 0.4% to 3%, in relation to the dry FOREIGN PATENTS weight of the binder, of the polyamide amine containing 721,332 9/ 1968 Belglllmrecurring cationic groupings are employed.

14. A process as in claim 5, in which cationic water WILLIAM MARTIN Primary Exammel soluble polyamides, which are produced by the poly- 1), COHEN, A i t E i alkylation of polymers of formula UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 l l 9 Dated December 26 1972 Inventor(s) HANNS JENNY, GEORGES KIESLINGER It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 66, someshould read same Coli nnn 4, line 21, "l' "',3"'-" should read --l"',3"',5'

Signed and sealed this 6th day of August 197 (SEAL) Attest:

MCCOY M. GIBSON, JR. 0. MARSHALL DANN Attesting Officer Commissioner of Patents ORM PO-IOSO (10-69) USCOMM-DC 6Q376-P5Q U45, GOVERNMENT PRINTING OFFICE I959 O365-33A. 

